Chemical Kinetics

Rates of Chemical Reactions

Chemical Kinetics
Kinetics - study of rates of chemical reactions
and the mechanisms by which they occur.
Reaction rate - increase in concentration of a
product per unit time or decrease in
concentration of a reactant per unit time.
Reaction mechanism - the series of molecular
steps by which a reaction occurs.
Kinetics versus Thermodynamics
Thermodynamics determines if a reaction can occur.
Kinetics determines how quickly a reaction occurs.
Some reactions that are thermodynamically
feasible are kinetically so slow as to be
imperceptible.
( ) ( )
( ) ( ) ( )
OUS INSTANTANE
kJ -79 = G O H OH + H
SLOW VERY
kJ 396 G CO O C
o
298 2
-
aq
+
aq
o
298 g 2 g 2 diamond
A
= A +
l
The Rate of Reaction
Consider the hypothetical reaction,
aA
(aq)
+ bB
(aq)
cC
(aq)
+ dD
(aq)
equimolar amounts of reactants, A and B, will be
consumed while products, C and D, will be
formed as indicated in this graph:
0
0.2
0.4
0.6
0.8
1
1.2
0
5
0
1
0
0
1
5
0
2
0
0
2
5
0
3
0
0
3
5
0
Time
C
o
n
c
e
n
t
r
a
t
i
o
n
s

o
f

R
e
a
c
t
a
n
t
s

&

P
r
o
d
u
c
t
s
[A] & [B]
[C] & [D]
[A] = concentration
of A in M ( mol/L).

Reaction does not
go entirely to
completion.
The [A] and [B] >
0 plus the [C] and
[D] < 1.
The Rate of Reaction
aA
(aq)
+ bB
(aq)
cC
(aq)
+ dD
(aq)


- Mathematically, the rate of a reaction can be
written as:


| | | | | | | |
t d
D +
t c
C +
or
t b
B -
t a
A -
= Rate
A
A
=
A
A
A
A
=
A
A
In terms of
reactants
In terms of
products
(aq) (aq) 9 4 ) l ( 2 (aq) 9 4
HCl OH H C O H Cl H C + +
[C
4
H
9
Cl]
(M) Time, t (s)
0.1 0
0.0905 50
0.082 100
0.0741 150
0.0671 200
0.0549 300
0.0448 400
0.0368 500
0.02 800
0.005 1500
0.0025 2250
0
0.02
0.04
0.06
0.08
0.1
0.12
0 500 1000 1500 2000 2500
[
C
4
H
9
C
l
]
,

M

Time, s
plot of [C4H9Cl] vs t
Average rate of reaction rate over a period of
time
| |
| | | |
( ) ( )
|
|
|
|
.
|

\
|

=
A
A
=
time initial time final
Cl H C Cl H C
t
Cl H C
Rate Average
time initial
9 4
time final
9 4
9 4
[C4H9Cl] (M) Time, t (s) Average rate
0.1 0
0.0905 50 0.00019
0.082 100 0.00017
0.0741 150 0.000158
0.0671 200 0.00014
0.0549 300 0.000122
0.0448 400 0.000101
0.0368 500 0.00008
0.02 800 0.000056
0.005 1500 2.14286E-05
0.0025 2250 3.33333E-06
Instantaneous rate of reaction rate at a
particular time
Instantaneous rate at 0
s Initial Rate
Instantaneous rate is actually the slope
(negative for reactants, positive for
products) of the tangent line passing
through the time t.
It is a derivative of the curve at that point.



INITIAL RATE
the instantaneous rate at t = 0
Important parameter being measured because it gives a
more accurate measure of rate
Changes when the initial concentration of reactant also
changes
| |
t
Cl H C
x
1
1
- = Rate
9 4
A
A
Rate Law Expressions / Rate Laws
The dependence of reaction rates to the
concentration of species is shown in a RATE
LAW expression (or simply rate law)

Rate = k[reactant
1
]
n
[reactant
2
]
m
...

m, n reaction orders (rate is nth order with
respect to reactant 1, mth order wrt reactant 2)
m + n overall reaction order
k rate constant a very important rate parameter,
as it describes how the reaction proceeds
Consider the following date for the
reaction:

2(g) (l) 2
-
3(aq) 4(aq)
N O 2H NO NH + +
+
Experiment #
Initial [NH
4
+
]
M
Initial [NO
3
-
]
M
Observed Initial Rate,
M/s
1 0.01 0.2 5.4 x 10
-7

2 0.02 0.2 10.8 x 10
-7

3 0.2 0.0202 21.6 x 10
-7

4 0.2 0.0404 43.3 x 10
-9

- as NH
4
+
doubles, the initial rate doubles!
- as NO
3
-
doubles, the initial rate also
doubles!
] NO [ ], [NH Rate
-
3 4
+

] NO ][ [NH k Rate
-
3 4
+
=
Types of reaction based on Rate law
Expressions
Reaction
Possible
Experimental
Rate Law
Order of Reaction
Unit of k (when t
in secs)
A products Rate = k Zero order M/s
A products Rate = k[A]
First order wrt [A],
First order overall
1/s
2A products Rate = k[A]
2

2nd order wrt [A],
2nd order overall
1/M-s
A + B products Rate = k[A][B]
1st order wrt [A],
1st order wrt [B],
2nd order overall
1/M-s
The following data were obtained for the
following reaction at 25
o
C. What are the rate-
law expression and the specific rate constant for
the reaction?
2 A
(g)
+ B
(g)
+ 2 C
(g)
3 D
(g)
+ 2 E
(g)


Experiment
Initial [A]
(M)
Initial [B]
(M)
Initial [C]
(M)
Initial rate of
formation of
D (M/s)
1 0.20 0.10 0.10 2.0 x 10
-4

2 0.20 0.30 0.20 6.0 x 10
-4
3 0.20 0.10 0.30 2.0 x 10
-4
4 0.60 0.30 0.40 1.8 x 10
-3
Differential Rate Law Forms
Reaction
Possible Experimental
Rate Law
Differential Rate law form
A products Rate = k
A products Rate = k[A]
2A products Rate = k[A]
2

A + B products Rate = k[A][B]
| |
k
t
A
=
A
A

| |
k[A]
t
A
=
A
A

| |
2
k[A]
t
A
=
A
A

| | | |
k[A][B]
t
B
t
A
=
A
A
=
A
A

Integrated Rate Law Equations

For a first-order reaction, the rate is
proportional to the first power of [A].



In Calculus

| |
| |
-
1
a
A
t
k A
A
A
|
\

|
.
|
=
| |
| |
-
1
a
A
t
k A
d
d
|
\

|
.
|
=
| |
| |
( )
-
A
A
a k t
d
d =
| |
| |
| |
| |
( )
-
A
A
a k t
A
A
t
d
d
0
0
}
=
}
This equation can be evaluated
as:
| |
| | | | ( ) ( )
| | | |
-ln A a k t or
-ln A A a k t - a k 0
which becomes
-ln A A a k t
t
0
t
t
t
0
0
0
=
+ =
+ =
ln
ln
First-Order integrated rate law
| |
| |
k t a
A
A
ln
t
0
=
- similar to the equation introduced for the half-life of
reactions in chem 16
- majority of simple nuclear decompositions/reactions
are first order process
| | | |
| | | |
0
0
A ln k t a A ln
or
k t a A ln A ln
+ =
=
Second-Order Integrated Rate Law
Only for second-order wrt [A] and 2nd order
overall
| |
| |
2
A k
t a
A
=
d
d
| |
| |
t k
A a
A
2
d
d
=
| |
| |
| |
| |
} }
=
t
0
A
A
2
t k a
A
A
0
d
d
| | | |
k t a
A
1
A
1
0
=
Second-Order Integrated Rate Law
Zero-Order Integrated Rate Law
| |
k
t a
A
=
d
d
| | t k a A d d =
| |
| |
| |
} }
=
t
0
A
A
t k a A
0
d d
| | | |
| | | | k t a - A A
or
k t -a A A
0
0
=
=
Integrated Rate Law Equations and
determination of Reaction Orders
Correlation with Linear Equation



If you are determining the order of reaction
for a particular reactant and you have a set of
concentration-time data (3 data points is
enough) wrt the reactant, then you can use
correlation with integrated rate laws.

b m y + = x
| | | |
0
A ln k t a A ln + =
| | | | k t a - A A
0
=
| | | |
0
A
1
k t a
A
1
+ =
b m y + = x
Concentration-versus-time data for the thermal
decomposition of ethyl bromide are given in the
table below. Use the following graphs of the
data to determine the rate of the reaction and
the value of the rate constant.
( ) ( ) ( )
700K at HBr H C Br H C
g g 4 2 g 5 2
+
A
Time
(min) 0 1 2 3 4 5
[C
2
H
5
Br] 1.00 0.82 0.67 0.55 0.45 0.37
| | | | k t a - A A
0
=
Time
(min) 0 1 2 3 4 5
1/[C
2
H
5
Br] 1.0 1.2 1.5 1.8 2.2 2.7
Time
(min) 0 1 2 3 4 5
ln [C
2
H
5
Br] 0.00 -0.20 -0.40 -0.60 -0.80 -0.99
| | | |
0
A ln k t a A ln + =
| | | |
0
A
1
k t a
A
1
+ =
[C
2
H
5
Br] vs. time
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5
Time (min)
[
C
2
H
5
B
r
]
ln [C
2
H
5
Br] vs. time
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 1 2 3 4 5
Time (min)
l
n

[
C
2
H
5
B
r
]
1/[C
2
H
5
Br] vs. time
0
1
2
3
0 1 2 3 4 5
Time (min)
1
/
[
C
2
H
5
B
r
]
Half-life of reactions, t
1/2
time when half of the initial
concentration of reactant is consumed.
To obtain half-life equation, just substitute [A] = [A]
0
when t
= t
1/2

| | | |
0
A ln k t a A ln + = | | | | ak t - A A
0
=
| | | |
0
A
1
k t a
A
1
+ =
| |
0
2
1
A ak
1
t =
2ak
A] [
t
0
2
1
=
ak
ln2
t
2
1
=
Sucrose, C
12
H
22
O
11
, which is commonly known as table sugar, reacts in
dilute acid solutions to form two simpler sugars, glucose and fructose.

C
12
H
22
O
11(aq)
+ H
2
O
(l)
2C
6
H
12
O
6(aq)


At 23
o
C and in 0.5M HCl, the following data were obtained for the
disappearance of sucrose:










(a) Determine the order of reaction and the rate law expression.
(b) What is the half-life for the conversion of sucrose into glucose and
fructose based on the conditions of analysis?
Time (min) [C
12
H
22
O
11
], M
0 0.316
39 0.274
80 0.238
140 0.190
210 0.146
Determination of Rate Laws
Write the general form of the rate law
expression (depends on the reactants present)
Determine the orders of reaction wrt each
reactant
Log-rate ratio technique
Initial rates and initial concentrations of reactants
integrated rate law technique
Concentration-time data
Determine the rate constant k

Experimental Methods of Determining
Rate Law
Initial Rates Method (Method of Initial Rates)
Initial rates of reaction are obtained
Time involved not > 5 minutes from start of
reaction
If time is given instead of rate, the rate can be is
approximated by 1/t
t
1
t
1
Rate
t
] tion [concentra
Rate

A

A
A
=
Consider the gas-phase reaction between nitric oxide and bromine at 273
o
C:

2NO
(g)
+ Br
2(g)
2NOBr
(g)


The following data for the time of appearance of NOBr were obtained:








(a) Determine the rate law
(b) Calculate the average value of the rate constant for the appearance of
NOBr.
(c) How is the rate of appearance of NOBr related to the rate of
disappearance of Br
2
?
(d) What is the rate of disappearance on Br
2
when [NO] =0.075 M and [Br
2
] =
0.185 M?
Experiment # [NO], M [Br
2
], M Time, sec
1 0.11 0.25 41.67
2 0.27 0.25 6.67
3 0.12 0.50 16.71
4 0.36 0.50 1.36
Experimental Methods of Determining
Rate Law
Pseudo-Order Systems (Isolation method)
The concentration of one of the reactants is
kept high and constant, so that the reaction
depends only on the variable reactant
concentration.
Only initial rates are measured
The reaction of peroxydisulfate ion, S
2
O
8
2-
, with iodide ion, I
-
, is given by
the equation :

S
2
O
8
2-
(aq)
+ 3I
-
(aq)
2SO
4
2-
(aq)
+ I
3
-
(aq)



At a particular temperature, the rate of disappearance of S
2
O
8
2-

varies with
reactant concentrations in the following manner:









(a) Determine the rate law for the reaction.
(b) What is the rate of disappearance of I
-
when [S
2
O
8
2-
] =0.075 M and [I
-
]
= 0.050 M?
[S
2
O
8
2-
], M [I
-
], M Rate, M/s
0.018 1.52 9.77 x 10
-5

0.027 1.53 1.48 x 10
-4

0.036 1.55 1.99 x 10
-4

0.79 0.015 4.23 x 10
-5

0.80 0.022 6.29 x 10
-5

0.81 0.037 1.07 x 10
-4

Factors That Affect Reaction Rates
There are several factors that can influence
the rate of a reaction:

1. The nature of the reactants.
2. The concentration of the reactants.
3. The temperature of the reaction.
4. The presence of a catalyst.


Nature of Reactants
Chemical properties of reactant affect rates
( ) ( ) ( ) ( )
burns. and ignites H - reaction rapid and Violent
H NaOH 2 O H 2 Na 2
2
g 2 aq 2 s
+ +

( ) ( )
( )
( )
( )
reaction. Slow
H OH Ca O H 2 Ca
g 2
aq
2 2 s
+ +

( ) ( )
eye human to e perceptibl Not
reaction No O H Mg
2 s
+

Acid-Base neutralizations, salt formation, and
precipitation reactions or ION-EXCHANGE
reactions are usually FASTER than reactions
involving COVALENT-bond breakage and formation.
Nature of Reactants
The Phase of reactants affect the rate of reaction
( ) ( )
eye human to e perceptibl Not
reaction No O H Mg
2 s
+

process fast Very
H MgO O H Mg
(g)
2 (s) ) ( 2 (s)
+ +
g
Homogenous reactions are faster than heterogenous
reactions

Heterogenous reactions with finely divided particles are
usually fast
Dissolution of panutsa versus plain table sugar.
Concentration of reactants



In the molecular level, increasing the
concentration of reactants means increasing
the chances of reactant encounters, or
COLLISIONS
Basic idea of COLLISION THEORY of reactions
Expression Law Rate from -
[reactant] Rate
Collision Theory of
Reaction Rates
Three basic events must happen for a
reaction to occur. The atoms, molecules or
ions involved must:
1. Collide.
2. Collide with enough energy to break and form
bonds.
3. Collide with the proper orientation for a
reaction to occur.
Collision Theory of
Reaction Rates
To increase chances/probability of collisions, |Temperature
(since |KE of particles as T increases)




Also, |T allows initial energy for bond breakage of reactant
molecules.

kJ 891 O H CO O CH
(g) 2 2(g)
,
2(g) 4(g)
+ + +
A matches
reaction) no added, heat (no O CH
2(g) 4(g)
+
Collision Theory of
Reaction Rates
Proper orientation of particles (upon collision) is also
necessary for formation of products to occur.



will product form in the following orientation of
molecules?
(g) 2 ) g ( 2 2(g)
O 2H O 2H +
(g) 2 ) g ( 2 2(g)
O 2H O 2H +
(g) ) g ( 2 2(g)
2HI I H +
Collision Theory only explains that successful
formation of products happens when
KE energy sufficient to form and break the
chemical bonds
correct orientation of molecules is achieved upon
collision

It gives an incomplete description of the
corresponding energy involved in the
rearrangement of atoms to form the final
compound
Transition State Theory
Transition state theory postulates that
reactants form a high energy intermediate,
the transition state, which then falls apart
into the products.

For a reaction to occur, the reactants must
acquire sufficient energy to form the
transition state.
This energy is called the activation energy or E
a
.

(g) ) g ( 2 2(g)
2HI I H +
Dependence of Rate on Temperature
Arrhenius Equation
Svante Arrhenius developed this relationship
among
(1) the temperature (T)
(2) the activation energy (E
a
), and
(3) the specific rate constant (k).
RT
E
- A ln = k ln
or
Ae = k
a
RT
E
-
a
K in e Temperatur T
K - mole
joule
8.314 constant gas R
energy Activation E
factor frequency A
constant rate k
Ae = k
a
RT
E
-
a

49
The Arrhenius Equation
If the Arrhenius equation is written for two
temperatures, T
2
and T
1
with T
2
>T
1
.
ln k ln A-
E
RT
and
ln k ln A-
E
RT
1
a
1
2
a
2
=
=
50
The Arrhenius Equation
Subtract one equation from the other.
ln k k A- ln A-
E
RT
E
RT
ln k k
E
RT
-
E
RT
2 1
a
2
a
1
2 1
a
1
a
2
=
|
\

|
.
|
=
ln ln
ln
|
|
.
|

\
|
=
|
|
.
|

\
|
=
1 2
1 2 a
1
2
2 1
a
1
2
T T
T - T
R
E
k
k
ln
or
T
1
T
1
R
E
k
k
ln
The temperature dependence of the rate
constant for the reaction

CO
(g)
+ NO
2(g)
CO
2(g)
+ NO
(g)


is tabulated below. Calculate E
a
and A.
Temperature, K k, M
-1
s
-1

600 0.028
650 0.22
700 1.3
750 6.0
800 23
Factors That Affect Reaction Rates
The presence of a catalyst.
May be included in the actual reaction, but is not
consumed in the process.
Catalysts change reaction rates by providing an
alternative reaction pathway with a lower E
a

Presence of Catalysts
Homogeneous catalysts exist in same phase as
the reactants.
Heterogeneous catalysts exist in different phases
than the reactants.
Catalysts are often solids.
( ) ( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( ) g 2 g 2
Pt and NiO
g
g 2
Pt and NiO
g 2 g
g 2 g 2
Pt and NiO
g 2 g 18 8
O N NO 2
CO 2 O + CO 2
O H 18 CO 16 O 25 + H C
+

+
Presence of Catalysts
( ) ( ) ( )
Process Haber
NH 2 H 3 N
g 3
O Fe or Fe
g 2 g 2
3 2
+
( ) ( )
( )
n preparatio acid Sulfuric
SO 2 O SO 2
g
3
NiO/Pt or O V
g 2 g 2
5 2
+
Molecularity of Reactions
Reaction Mechanisms
Reaction mechanism - the series of
molecular steps by which a reaction
occurs.
The molecular steps proposed should add
back to final balanced equation
It must be CONSISTENT with the RATE LAW
obtained for the actual reaction (remember
rate law is derived from experimental results)
Molecularity of Reactions Reaction
Mechanisms
( ) ( ) ( ) ( )
| || | NO O k = Rate : law Rate al Experiment
O + NO NO + O
3
g 2 g 2 g g 3

The mechanism that you propose should be simple
and consistent with the overall reaction
2 2 3
2 2 3
3 3
O + NO NO + O reaction Overall
O + NO NO + O step Fast
O + NO NO + O step Slow

-Each step in the proposed mechanism is called an

ELEMENTARY STEP or ELEMENTARY reaction

- For each elementary step, the rate law is based on the
reactants present and the order is the same as the actual
stoichiometric coefficient as shown in the reaction
2 2 3
2 2 3
3 3
O + NO NO + O reaction Overall
O + NO NO + O step) (fast 2 Step
O + NO NO + O step) (slow 1 Step
2
1

k
k
] [O][NO rate : 2 Step
][NO] [O rate : 1 Step
3 2 2
3 1 1
k
k
=
=
- The elementary step that is assigned as SLOW STEP will dictate
the actual rate law for the entire reaction
- SLOW step dictates the rate law because it is the main
bottle neck of the entire reaction
- The rate constant k
1
is the actual rate constant obtained
in the experiment

| || | NO O rate : 1 Step
3 1 1
k =
( ) ( ) ( ) ( ) g 2 g 2 g g 3
O + NO NO + O
| || | NO O k = Rate
law Rate al Experiment
3
The proposed mechanism is consistent and
therefore a possible reaction pathway
A mechanism that is inconsistent with the rate-law
expression is:
Experimentally determined reaction orders indicate
the number of molecules involved in:
1. the slow step only or
2. the slow step and the equilibrium steps preceding
the slow step.
| |
correct. be cannot mechanism this proves which
O k = Rate is mechanism this from law - rate The
O NO NO + O reaction Overall
NO NO + O step Fast
O + O O step Slow
3
2 2 3
2
2 3
+

The proposed mechanism for the substitution of OH

-
with Br
-
in
tertbutyl bromide is shown below
( ) ( ) aq
-
(aq) 3 3
aq
-
(aq) 3 3
Br + COH ) CH ( OH + CBr ) CH (
O H COH ) (CH OH COH ) (CH (3)
COH ) (CH O H C ) CH ( ) 2 (
Br + C ) CH ( CBr ) CH ( (1)
2 3 3 2 3 3
2 3 3 2 3 3
-
3 3 3 3
3
2
1
+ +
+

+
+
+
+
k
k
k
1. Determine the slow step if the experimental rate law
obtained is rate = k[(CH
3
)CBr]
2. Identify the intermediates in the proposed reaction
mechanism
3. Identify the catalysts in the system
4. Give the equation for the dependence of E
a
with the
reaction constants of the proposed mechanism
( ) 2(g) g 2 (g)
NO 2 O + 2NO
(slow) NO 2 O O N (2)
m) equilibriu (fast, O N 2NO (1)
2 2 2 2
2 2
2
) ( ' 1
) ( 1
+


k
k
k
backward
forward
A consistent mechanism proposed for the oxidation
of nitrous oxide into nitrogen dioxide is shown below.
1. Identify the intermediates in the proposed reaction
mechanism
2. Determine the expected rate law for this mechanism
(Hint: Equilibrium systems indicate rates of forward and
backward steps to be constant)
3. Give the equation for the dependence of E
a
with the
reaction constants of the proposed mechanism